WO2017036743A1

WO2017036743A1 - Organosilicon compounds having (meth)acrylate groups and a process for preparation thereof

Info

Publication number: WO2017036743A1
Application number: PCT/EP2016/068945
Authority: WO
Inventors: Elke Fritz-Langhals
Original assignee: Wacker Chemie Ag
Priority date: 2015-09-04
Filing date: 2016-08-09
Publication date: 2017-03-09
Also published as: DE102015216951A1; JP6685386B2; US20180201633A1; JP2018522934A; US10329313B2; CN107922442B; KR102063238B1; EP3344634B1; EP3344634A1; KR20180044414A; CN107922442A

Abstract

The invention provides (meth)acrylate-functional organosilicon compounds M where the (meth)acrylate group is bonded to the silicon of the organosilicon compound via an oxygen atom, wherein the carbon atom bonded to the oxygen atom bears at least one further carbon-bonded radical, with the proviso that, in the presence of only one further radical, the latter contains more than one carbon atom, to a process for preparation thereof via (meth)acrylate-functionalized chlorosilanes, and to the (meth)acrylate-functionalized chlorosilanes.

Description

(Meth) acrylate group-containing organosilicon compounds and a process for their preparation

The invention relates to (meth) acrylate groups

Organosilicon compounds, a simple process for their preparation via (meth) acrylate-functionalized chlorosilanes and the (meth) acrylate-functionalized chlorosilanes.

Organosilicon compounds containing (meth) acrylate groups play an important role in many areas of the art. For example, silicone materials can be cured via the (meth) acrylate groups. Such materials are used i.a. needed for the production of abhesive coatings by radiation curing. The (meth) acrylate group can also be copolymerized with other (meth) acrylates as desired, so that new materials with tailored properties are accessible in this way. In all of these materials, long-term stability plays an important role. (Meth) acrylate-functional organosilicon compounds are already known. As a rule, the (meth) acrylate moiety is linked to the siloxane skeleton via a carbon spacer. This Si-C linkage is always via a

Noble-metal-catalyzed addition of organosilicon compounds containing Si-H groups to olefins, a so-called

Hydrosilylation, achieved. However, the introduction of the (meth) acrylate group must be carried out in a subsequent further step, otherwise unwanted side reactions under

Participation of the (meth) acrylate double bond occur.

The Si-C-linked (meth) acrylate-functional organosilicon compounds can be prepared, for example, as described in US Pat. No. 4,978,726 by initially containing Si-H-containing organosilicon compounds with a olefinic epoxide, such as allyl glycidyl ether, are reacted, and then the (meth) acrylate moiety is attached by epoxide ring opening.

Another method described in US-4963438 is that the Si-H moiety is first added to an olefinic alcohol, for example allyl alcohol, and then the attachment of the (meth) acrylate moiety by esterification with the hydroxy group.

A disadvantage of these methods is that they each contain a noble metal-catalyzed and therefore expensive reaction step, the hydrosilylation. In addition, it is disadvantageous in these processes that the attachment of the (meth) acrylate moiety must take place in a downstream polymer-analogous step. In addition, in particular the reactions with acrylic acid are associated with the formation of by-products, which can not be removed from the polymer or only at great expense.

For example, US Pat. No. 4,301,268 and US Pat. No. 4,306,050 also disclose Si-O-C-linked (meth) acrylate-functional polysiloxanes which are prepared by reacting chloropolysiloxanes with (meth) acrylate-functional alcohols. However, stand

Chloropolysiloxanes as industrial products not to

Available, since they have only a limited shelf life. However, as described in DE 10359764, these compounds are not sufficiently stable to hydrolysis. However, the long-term hydrolytic stability of the linker moiety is an important prerequisite for the long-term stability of the products and thus for their technical applicability.

The previously known Si-OC-linked (meth) acrylate-functional organosilicon compounds are particularly susceptible to hydrolysis if they contain salts, especially in the form of chlorides, from synthesis. This problem is solved in DE 10359764 and in EP 1595909 by reacting H-siloxanes and acrylate-functional alcohols in the presence of a Lewis acid as catalyst for the synthesis. In this approach, however, is a disadvantage that relatively expensive H-siloxanes must be used, and also that in the reaction hydrogen is formed, which requires complex safety measures. The Lewis acids used are preferably very expensive perfluorinated organoboron compounds, which can no longer be removed from the polymer due to their low volatility, thus remaining in the end products and thus posing an environmental problem.

There is therefore a need for (meth) acrylate-functional organosilicon compounds which can be prepared in a simple and inexpensive way. In particular, compounds of interest, which can be produced via a hydrosilylierungsfreien way without using expensive catalysts. Another important requirement for industrial use is that the (meth) acrylate-functional organosilicon compounds are stable to hydrolysis even in the presence of impurities.

The invention relates to (meth) acrylate-functional

Organosilicon compounds M in which the (meth) acrylate group is bonded via an oxygen atom to the silicon of the organosilicon compound, wherein the carbon atom bound to the oxygen atom carries at least one further carbon-bonded radical, with the proviso that in the presence of only one more rest of this more than one

Contains carbon atom. Surprisingly, it has been found that these (meth) acrylate-functional organosilicon compounds M are stable to hydrolysis even in the presence of impurities. The term (meth) acrylate means methacrylate, acrylate or a mixture of methacrylate and acrylate.

Preferably, the (meth) acrylate-functional Organosiliciuraverbindungen M are composed of at least one unit of general formula I and none or at least one

Unit of general formula II

R ² bX _c SiO [4- (b ₊ c)] / 2 (I) /

R _a SIO (4 _-a) / 2 (II) wherein

R ¹ and R ^{2 are} independently hydrogen or unsubstituted or substituted with substituents selected from -CN, NR ^X ₂ , COOH, COOR, halo, acrylic, methacryl, - epoxy, -OH and -CONR ^x ₂ substituted C ₁ -C 20 -hydrocarbon radicals or C 1 -C -hydrocarboxyoxy radicals, in each of which one or more, mutually non-adjacent methylene units are replaced by groups -O-, -CO-, -COO-, -OCO- or -OCOO or NR ^X can,

R ^{x is} hydrogen or an unsubstituted or with substituents which are selected from -CN and halogen, substituted Ci-Cio - hydrocarbon radical,

X is an oxygen-bonded radical of the general

Formula (III)

0-C (R ³ R ⁴ ) -R ⁵ -O- (C = O) -CR ⁶ = CH ₂ ) (III)

R ³ and R ⁴ independently of one another are hydrogen or C ₁ -C ₂ 0 -hydrocarbon radicals, in each of which one or more non-adjacent methylene units may be replaced by groups 0- (C = O) -CR ⁶ = CH ₂ , -O-, -CO-, -COO-, -OCO-, -OCOO- or NR ^X , with the proviso that if R ³

Is hydrogen, R ^{4 contains} at least two carbon atoms,

R ⁵ divalent Ci-C ₂₀ -hydrocarbon radical, in each case one or more, not adjacent to each other

Methylene units may be replaced by groups -0-, -CO-, -COO-, or -OCOO- -0C0- or NR ^X,

R ^{6 is} hydrogen or straight-chain, branched or cyclic saturated or unsaturated alkyl group having 1 to 12 C atoms or aryl group or aralkyl group, where individual non-adjacent methylene units may be replaced by nitrogen atoms or oxygen atoms,

a is 0, 1, 2 or 3,

b the values 0, 1 or 2,

c the values 1, 2 or 3 and

b + c is 1, 2, 3 or 4.

R ¹ and R ² preferably have 1 to 12 atoms in the skeleton,

in particular 1 to 6 atoms, preferably only carbon atoms or an alkoxy oxygen atom and otherwise only carbon atoms and hydrogen atoms. Preferably, R ¹ and R ^{2 are}

straight-chain, branched or cyclic C ₁ -C ₆ -alkyl or

Alkoxy. Particularly preferred are the radicals methyl, ethyl, phenyl, vinyl, trifluoropropyl, methoxy, ethoxy and i-propoxy. The radicals R ¹ and R ² may be the same or different on the same silicon atom.

R ³ and R ⁴ preferably have 1 to 12 carbon atoms, especially 1 to 6 carbon atoms, preferably only

Carbon atoms or oxygen atoms or only carbon atoms. If R ^{3 is} a hydrogen atom then R ⁴ must be at least have two carbon atoms. Preferably, R ³ and R ^{4 are} straight-chain, branched or cyclic Cx - Cg-alkyl radicals or aryl radicals, which may contain one or more further (meth) acrylate groups, particularly preferably the radicals methyl, ethyl and (meth) acryloxymethyl.

Particularly preferably, the two radicals R ³ and R ^{4 are} each methyl.

The radical R ⁵ is preferably a divalent C-bonded Οχ-C ₆ hydrocarbon radical in which non-adjacent

Methylene groups may be replaced by oxygen.

Preferably, R ^{5 is} a straight-chain or branched one

Alkylene radical. Particularly preferred are the alkylene radicals

Methylene, ethylene, propylene or butylene.

R ⁶ is preferably hydrogen or straight-chain, branched or cyclic saturated or unsaturated alkyl group having 1 to 6 C atoms or aryl group.

R ⁶ is particularly preferably hydrogen or C ¹ -C ₅ -alkyl, very particularly preferably R ^{6 is} hydrogen.

Preferably, c is 1.

The meth) acrylate-functional organosilicon compounds M can be linear, branched, cyclic, bicyclic, tricyclic or polycyclic. It can be oils, resins or

Particles act.

The (meth) acrylate-functional organosilicon compounds preferably contain from 1 to 20, in particular from 2 to 10, units of the general formula I. The (meth) acrylate-functional organosilicon compounds preferably contain 1 to 500, more preferably 4 to 200, in particular 10 to 100 units of the general formula II.

Preferably, at least 90%, in particular at least 95% of the units of the general formula II a is 2.

Examples of groupings X are:

OC (CH ₃ ) ₂ -CH ₂ -O- (C = O) -CH = CH ₂

0-C (CH ₃ ) ₂ -CH (CH ₃ ) -O- (C = O) -CH = CH ₂

0-C (CH ₃₎ 2 -CH ₂ -CH ₂ -0- (C = 0) -CH = CH ₂

0-C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) -O- (C = O) -CH = CH ₂

0-CH (C ₂ H ₅ ) -CH ₂ -O- (C = O) -CH = CH ₂

O-CH [CH ₂ O- (C = O) -CH = CH ₂ ] 2

Another object of the invention is a process for preparing the (meth) acrylate-functionalized organosilicon compounds M composed of at least one unit of the general formula I and no or at least one unit of the general formula II

R bXcSiO [ _4- (b + _C )] / 2 ⁽ I),

in the (meth) acryloyl-functionalized chlorosilanes of the general formula IV

R _b X _c SiCl [4- (b + c)] (IV) are reacted with hydroxy-functionalized organosilicon compounds,

wherein R ¹ , R ² , X, a, b and c have the above meanings and preferred meanings. Another object of the invention is a process for preparing the (meth) acrylate-functionalized chlorosilanes of the general formula IV

R ² _b X _c SiCl [ ₄ _ (b + c)] (IV),

in the (meth) acryloyl - functionalized alcohols of the

general formula V

HO-C (R ³ R ⁴ ) -R ⁵ -O- (C = O) -CR ⁶ = CH ₂ (V) with chlorosilanes of the general formula VI

R ² _b SiCl _[4 - _b ] (VI) are reacted,

wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, b and c have the above meanings and preferred meanings.

Another object of the invention are also (meth) acryloyl-functionalized chlorosilanes of the general formula IV R ² _b X _c SiCl [4- ( _{b +} c)] (IV) wherein R ² , X, b and c are as defined above and

have preferred meanings. The (meth) acrylate-functionalized organosilicon compounds

M can thus be prepared from industrially available organosilicon compounds such as hydroxypolysiloxanes or hydroxypolysiloxanes mixed with siloxane cycles using the (Meth) acryloyl-functionalized chlorosilanes of the general formula IV are prepared.

For the (meth) acrylate-functionalized organosilicon compounds M, no technically suitable simple production process existed so far.

EP 1544232 describes the preparation of (meth) acrylate-functionalized polysiloxanes which are linked to the silicon via an oxygen atom by dehydrogenating

Linkage of a hydride-functional siloxane and a

Hydroxy-functional acrylate using Lewis acids, in particular perfluorinated organoboron compounds as catalysts. This synthetic route uses a very expensive catalyst that can not be removed from the product. In addition, the formation of hydrogen during the reaction also poses high safety requirements.

The documents US 4301268 and US 4306050 also describe the preparation of Si-O-C-linked (meth) acrylate-functional polysiloxanes by reacting chloropolysiloxanes with

(Meth) acrylate-functional alcohols. However, stand

Chloropolysiloxanes as industrial products not to

Available, since they have only a limited shelf life.

There is therefore a need for a simple and inexpensive process for the preparation of (meth) acrylate-functional Si-O-C-linked organosilicon compounds.

In particular, a process would be advantageous in the case of the large-scale organosilicon compounds which are available in stable form, for example hydroxypolysiloxanes or .alpha

Hydroxypolysiloxanes in mixture with siloxane cycles used could become.

It has surprisingly been found that the (meth) acrylate-functional Si-O-C-linked organosilicon compounds M can be readily prepared from (meth) acryloyloxy-functionalized chlorosilanes. These are easily accessible from the (meth) acryloyloxy-functional alcohols and alkylchlorosilanes. The (meth) acrylate-functional alcohols of general formula V used can be prepared in a manner known to those skilled in the art, for example by esterification of di- or polyols and (meth) acryloyl chloride in the presence of a base, e.g. Triethylamine or by azeotropic esterification of diols with (meth) acrylic acid. If two or more

chemically identical hydroxy groups are present, the

Degree of conversion by the amount of (meth) acrylic acid or

(Meth) acrylic acid chloride based on the number of hydroxyl groups present are controlled. For di- or polyols with chemically different hydroxyl groups, the esterification is carried out i.A. regioselectively preferred at the sterically less hindered position, i. for example, to a primary or secondary alcohol moiety, preferably to a tertiary alcohol moiety.

Examples of the alcohols used in the preparation of the (meth) acryloyl-functionalized alcohols of the general formula V are 2-methyl-1,2-propanediol, 2-methyl-2, 3-butanediol, 3-methyl-1,3-yl butanediol, 2-methyl-2-pentanediol, 1, 2-butanediol and glycerol.

Another possible method of preparation of the (meth) acrylate-functional alcohols V is the ring-opening of epoxides with (meth) acrylic acid or its salts, for example the Reaction 2, 2-dimethylethylene oxide with acrylic acid, which is described in WO 2013096587.

The reaction of the (meth) acrylate-functional alcohols of the general formula V with chlorosilanes of the general formula VI to the (meth) acrylate-functional chlorosilanes of the general formula IV can be carried out as a batch reaction, as a semi-batch reaction or continuously. Preferably, the chlorosilane of the general formula VI is initially charged, if appropriate in an inert solvent, and the (meth) acrylate-functional alcohol of the general formula V, likewise where appropriate in an inert solvent,

dosed.

As inert solvents, for example, toluene, methyl tert. butyl ether, dichloromethane, cyclohexane or mixtures thereof. The proportion of inert solvent is preferably at least 5% by weight and at most 1000% by weight, preferably at least 20% by weight and at most 300% by weight, more preferably at least 50% by weight and at most 200% by weight, based on the reaction mass from the general formula chlorosilane VI and (meth) acrylate-functional alcohol of the general formula V without solvent. The (meth) acrylate-functional alcohol of the general formula V is preferably in molar excess based on all im

Chlorosilane of the general formula VI existing chlorine groups used so that at least one Si-Cl unit is present after the reaction.

For example, in tetrachlorosilane, at least 0.8 and at most 3.3 equivalents, particularly preferably at least 1.0 and at most 2.2 equivalents of (meth) acrylate-functional alcohol of the general formula V are preferably used, in the case of trichlorosilanes, preferably at least 0.8 and at most 2.2 equivalents, more preferably at least 1.0 and at most 1.2 equivalents,

for dichlorosilanes, preferably at least 0.8 and at most 1.3 equivalents, preferably at least 0.9 and at most 1.2 equivalents.

The reaction preferably takes place to bind the hydrogen chloride formed in the presence of a base, preferably in the presence of ammonia or an organic amine base, for example triethylamine or tributylamine.

The base is preferably added to the (meth) acrylate-functional alcohol of the general formula V. Another

Possibility to add the base separately.

The base is preferably used in proportions of at least 0.8 equivalents and at most 1.3 equivalents, more preferably in proportions of at least 0.9 equivalents and at most 1.2 equivalents, based on the alcohol grouping of

used (meth) acrylate-functional alcohol of

general formula V used.

The reaction time is preferably at least 1 min. and at most 50 hours, more preferably at least 30 minutes and at most 20 hours, especially preferably

at least 1 hour and at most 10 hours ..

The reaction is preferably carried out at temperatures between 0 and 180 ° C., particularly preferably between 20 and 120 ° C., and pressures preferably between 100 mbar and 10 bar, more preferably between 1 and 5 bar. The obtained (meth) acrylate-functional chlorosilanes of the general formula IV are reacted with hydroxy-functional siloxanes to give the (meth) acrylate-functional polysiloxanes M. This reaction can be carried out as a batch reaction, as a semi-batch reaction or continuously. Preferably, the hydroxy-functional siloxane is initially charged, optionally in dilute form, and the (meth) acrylate-functional chlorosilane IV also optionally in

diluted form, dosed.

For dilution, for example, inert solvents such as toluene, methyl tert. butyl ether, dichloromethane, cyclohexane or mixtures thereof. The proportion of inert

Solvent is preferably at least 5 wt.% And at most 1000 wt.%, Preferably at least 20 wt.% And at most 300 wt.%, Particularly preferably at least 50 wt.% And at most 200 wt.%, Based on the used

Hydroxypolysi1oxan.

The (meth) acrylate-functional chlorosilane of the general

Formula IV is preferably used in molar proportions of at least 0.2 equivalents and at most 3.0 equivalents, preferably 0.8

Equivalents and at most 2 equivalents, particularly preferably at least 1.0 equivalents and at most 1.3 equivalents, based on the hydroxypolysiloxane present in the hydroxy groups used.

Preferably takes place. the reaction for binding the hydrogen chloride formed in the presence of a base, preferably in the presence of ammonia, an organic amine base, or a

Alkali, alkaline earth or earth metal carbonate, bicarbonate or hydroxide. Examples of bases used are potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, ammonia, triethylamine or tributylamines.

The base is preferably added to the hydroxypolysiloxane. Another option is to add the base separately. The base is preferably used in proportions of at least 0.8 equivalents and at most 1.3 equivalents, more preferably in proportions of at least 0.9 equivalents and at most 1.2 equivalents, based on the existing Chlorsilangruppie- ments.

The reaction time is preferably at least 10 minutes. and at most 200 hours, more preferably at least 1 hour and at most 100 hours, particularly particularly preferably at least 1 hour and at most 70 hours.

In a special, (meth) acrylate-functional monochlorosilanes of the general formula IV with b + c = 3 preferred embodiment, these are converted with water into the corresponding disiloxanes of the general formula formula I with b + c = 3:

2 R ² _b X _c SiCl + H ₂ O => R ² _b X _c Si-O-SiXR ² _b + 2 HCl which are then reacted with terminally hydroxy-functionalized organosilicon compounds or siloxane cycles or mixtures of these in an equilibration reaction to the corresponding (Meth) acrylate-functional polysiloxanes M are reacted.

The reaction with water takes place here to neutralize the hydrochloric acid formed, preferably in the presence of a base, preferably in the presence of an alkali metal or alkaline earth metal hydrogen carbonate, carbonate or hydroxide, or in

Presence of ammonia.

The chlorosilane is preferred with at least 0.5 equivalents of water and at most 100 equivalents of water, especially preferably with at least 1 equivalent of water and at most 30 equivalents of water at temperatures between at least 0 and at most 180 ° C, more preferably between at least 20 and at most 120 ° C, and pressures preferably between at least 10 mbar and at most 10 bar, more preferably between at least 100 mbar and not more than 2 bar implemented.

The disiloxane obtained can be used before further reaction with the hydroxy-functional polysiloxane without further purification or else be purified. For purification, excess water is removed from the crude product, optionally by distillation or extraction of the product with an inert solvent, optionally formed salts are separated, optionally by extraction with water, by filtration or by distillation of the solvent.

The reaction with the hydroxy-functional polysiloxane or with siloxane cycles, a so-called equilibration reaction, can be carried out in a manner known to those skilled in the art.

All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

In the following examples, unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) And all temperatures are 20 ° C.

Example 1 (not according to the invention)

(Synthesis of 2-hydroxy-2-methylpropyl acrylate precursor)

Under inert gas, triethylamine (66.8 g, 91.5 mL, 0.66 mol, 1.2 eq.) And 2-methylpropane-1, 2 -diol (49.6 g, 0.55 mol, 1 eq.) Submitted in 300 mL dichloromethane and with an ice bath to 0 Cooled ° C. Via a dropping funnel, a solution of 200 mL dichloromethane and acryloyl chloride (49.8 g, 44.5 mL, 0.55 mol, 1 eq.) Within one hour at room temperature

dropwise. This gradually formed a colorless

Rainfall. The reaction solution was allowed to rise overnight

Room temperature heated and then the resulting

Precipitate filtered off. The reaction solution was washed twice with 100 ml of water each time and dried over MgS0 ₄ .

Subsequently, the solvent was removed on a rotary evaporator and the crude product distilled in vacuo. Sdp. 43-44 ° C / 7.7-8.4 10 ^"1 mbar, giving 50.7 g (71%) of the pure product as a colorless-clear liquid, stored at 7 ° C, stabilized with -methoxyphenol.

¹ H-NMR (CDCl ₃ ): δ = 1.21 (s, 6H, CH ₃ ), 2.30 (br s, 1H, OH), 3.99 (s, 2H, CH ₂ ), 5.81 (dd, ³ J ^" H, _h = 10.5 Hz, 1.5 Hz, 1H) 6.12 (dd,

³ J _H , _h = 10.5 Hz, 1.7 Hz, 1H), 6.39 ppm (dd, ³ J ^" _H , _H = 1.5 Hz, 17 Hz, 1H).

¹³ C-NMR (CDCl ₃ ): 5 = 26.05 (2C, CH ₃ ), 69.72 (IC, OOH), 72.01 (IC, CH ₂ ), 127.99 (IC, HC = CH ₂ ), 131.19 (IC, HC = _CH2), 166.08 ppm (IC, ROC = 0).

Example 2 [(chlorodimethylsilyl) oxy)] -2-methylpropyl acrylate (formula III, R ² = R ³ = R ⁴ = Me, R ^B = CH ₂ , R ⁶ = H, b = 2, c = 1)

22.4 g (0.17 mol) of dichlorodimethylsilane were dissolved under argon in Presented piston. 5.00 g (35 mmol) of 2-hydroxy-2-methylpropyl acrylate, 4.05 g of triethylamine (40 mmol) and 10 ml of dry methyl tert-butyl ether were mixed under argon and added dropwise with ice cooling within one hour to dichlorodimethylsilane. After a reaction time of 2 hours, the

Removed ice bath and the reaction continued at room temperature overnight. After completion of the reaction, the crude product was distilled. This gives 5.8 g (71%) of a clear colorless liquid with SD. 41-44 ° C / 0.41 mbar. Stabilization by adding 4-methoxyphenol and storage at 4 ° C in the refrigerator.

^ -NMR (CDCl ₃ ): 5 = 0.296 (s, 6H, (CH ₃ ) ₂ SiCl), 1.21 (s, 6H, CH ₃ ), 3.89 (s, CH ₂ ), 5.69 (dd, J _H , H = 10.5 Hz, 1.5 Hz, 1H), 6.00 (dd, JH, H = 10.5 Hz, 17.5 Hz, 1H), 6.28 ppm (dd, J _H, H = 1-5 Hz, 17.5 Hz, 1H).

¹³ C-NMR (CDCl ₃ ): δ = 4.57 (2C, Si (CH ₃ ) ₂ Cl), 26.79 (2C, CH ₃ ), 71.53 (IC, CH ₂ ), 75.21 (IC, C (CH ₃ ) ₂ ), 128.28 (IC, HC = CH ₂ ),

130.97 (IC, HC = CH ₂ ), 165.84 ppm (IC, ROC = 0).

2 ⁹ Si NMR ^' (CDCl 3) δ = 4.88 ppm ((CH ₃ ) ₂ SiCl).

Example 3: Acrylate-Functional Polysiloxane

138 g (0.141 mol) of a terminally functionalized with a hydroxy-functional polysiloxane (MW 980, chain length n = 13) were mixed with 150 ml of methyl tert. butyl ether and treated with 17.1 g (0.169 mmol) of triethylamine. Under argon, 40.0 g (0.169 mol) of [(chlorodimethylsilyl) oxy)] -2-methylpropyl acrylate (Formula III, R ² = R ³ = R ⁴ = Me, R ⁵ = CH ₂ , R ⁶ = H, b = 2, c = 1) was added and the mixture at 72 hrs

Room temperature stirred with exclusion of light. The educated as Solids accumulating ammonium salt was filtered off. The organic phase was evaporated and concentrated on a

Short-path evaporator volatilized at 70 ° C / 4,2'10 ^{~ 2} mbar.

Yield 134 g (85.1%).

1 H NMR (CDCl ₃ ): δ = 0.025-0.150 (m, 72 H, Si (CH ₃ ) ₂ ), 1-29 (s,

6H, CH ₃ ), 3.99 (s, 2H, CH ₂ ), 5.81 (dd, J ^" _H , H = 10 Hz, 1.5 Hz, 1H), 6.13 (dd, J _H , _h = 10 Hz, 17 Hz, 1H), 6.41 ppm (dd, J ^" _H , _H = 1.5 Hz, 17.5 Hz, 1H).

¹³ C-NMR (CDC1 _3): 5 = 1:04 to 1:13 (m, Si (CH ₃₎ _2), 1.70 - 1.81 (m, Si (CH ₃₎ _2), 26.97 (2C, CH _3), 72.16 (IC , CH ₂ ), 72.91 (IC,

CH ₂ C (CH ₃ ) ₂ ), 128.53 (IC, HC = CH ₂ ), 130.64 (IC, HC = CH ₂ ), 165.99 ppm (IC, ROC = 0).

²⁹ Si NMR (CDCl ₃ ): δ = -22.07 - -21.93 (11 Si, (CH ₃ ) Si), -21.39 (ISi, (CH ₃ ) ₃ SiOSi (CH ₃ ) ₂ ), -18.71 (1 Si , (CH ₃₎ ₂ COSi (CH ₃₎ ₂ 0), 7.25 ppm (1 Si, (CH ₃₎ ₃ Si).

Example 4: Stability of the acrylate-functional polysiloxane from Example 3 in water

0.7 ml of the acrylate-functional polysiloxane from Example 3 were stirred with 0.9 ml of water for a total of 8 days at room temperature and the two phases were analyzed separately by NMR spectroscopy. There was no detectable hydrolytic

Cleavage reaction. Example 5 Non-Water-Stable Not According to the Invention

acrylate

0.78 g of acrylate-functional polysiloxane having the formula

(CH ₃₎ ₃ Si-0- [Si (CH ₃₎ ₂ -O] n Si (CH ₃₎ ₂ -0-CH ₂ -CH ₂ -OCO-CH = CH ₂ and 0.9 g of water at Room temperature for 2 h. Stirred and the

Polymer phase ^ ^"H-NMR spectroscopy with the addition of trichloro- acetylisocyanat as a derivatizing reagent for Si-OH groups studied. It was the formation of 20 mol% Si-OH

Chain ends are detected.

Claims

Claims:

1. (meth) acrylate-functional organosilicon compounds M in which the (meth) acrylate group is connected via an oxygen atom to the silicon of the organosilicon compound, wherein the carbon atom bound to the oxygen atom carries at least one further carbon-bonded radical, with the proviso that in the presence of only one more remainder of these more than one

Contains carbon atom.

2. (meth) acrylate-functional organosilicon compounds M according to claim 1, composed of at least one unit of the general formula I and no or at least one unit of the general formula II

R bXcSiO [4_ (b ₊ c)] 12 (I ⁾ ,

R _a SIO (4 _-a) / ₂ (II) wherein

R ¹ and R ² independently of one another are hydrogen atoms or unsubstituted or having substituents which are selected from -CN, NR ^X ₂ , COOH, COOR ^x , -halo, -acryl, methacryl, -epoxy, -OH and -CONR ^x ₂ substituted Ci-C ₂ o -Kohlenwasser- radicals or 0 -0 ₁₅ _Χ -hydrocarbonoxy radicals, in each of which one or more nonadjacent methylene units by groups -0-, -CO-, -COO-, -OCO- or -0C00 or NR ^X can be replaced,

X is an oxygen-bonded radical of the general

Formula (III) 0-C (R ³ R ⁴ ) -R ⁵ - 0 - (C = O) - CR ⁶ = CH ₂ ) (III)

R ³ and R ⁴ independently of one another are hydrogen or C ₁ -C 20 -hydrocarbon radicals, in each of which one or more, non-adjacent methylene units are represented by groups

0- (C = 0) -CR ⁶ = CH _2, -O-, -CO-, -COO-, -OCO- or -OCOO- or NR ^X may be replaced, with the proviso that when R ³ is hydrogen , R ^{4 contains} at least two carbon atoms,

Methylene units may be replaced by groups -O-, -CO-, -COO-, -OCO- or -OCOO- or NR ^X ,

R ^{6 is} hydrogen or unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 12 C

Atoms or aryl group or aralkyl group, where individual non-adjacent methylene units may be replaced by nitrogen atoms or oxygen atoms,

a is 0, 1, 2 or 3,

b the values 0, 1 or 2,

c the values 1, 2 or 3 and

b + c is 1, 2, 3 or 4.

3. (meth) acrylate-functional organosilicon compounds M according to claim 2, in which R ¹ and R ^{2 are} straight-chain,

branched or cyclic Ci-C ₃ alkyl or alkoxy radicals, or phenyl or vinyl radicals.

4. (meth) acrylate-functional organosilicon compounds M according to one or more of claims 2 or 3, in which

R ³ and R ^{4 are} selected from methyl, ethyl and

(Meth) acryloxymethyl. (Meth) acrylate-functional organosilicon compounds M according to one or more of claims 2 to 4, wherein R ^{5 is} a divalent C-bonded Cx -Cg hydrocarbon radical, in which non-adjacent methylene groups may be replaced by oxygen.

Process for the preparation of (meth) acrylate-functionalized organosilicon compounds M according to one or more of claims 2 to 5, composed of at least one unit of general formula I and no or at least one unit of general formula II

R _b X ₀ SiO [4_ <b + c)] / 2 (I) /

in the (meth) acryloyl-functionalized chlorosilanes of the general formula IV

R bX _c SiCl [ ₄ ( _{b + C)} ] (IV) are reacted with hydroxy-functionalized organosilicon compounds,

wherein R ¹ , R ² , X, a, b and c have the meanings according to one or more of claims 2 to 5.

Process for the preparation of the (meth) acrylate-functionalized chlorosilanes of the general formula IV according to Claim 6

R bXcSiCl [4_ (b + c)] (IV), in the (meth) acryloyl-functionalized alcohols of the general formula V

HO-C (R ³ R ⁴ ) -R ⁵ -O- (C = O) -CR ⁶ = CH ₂ (V)

Chlorosilanes of the general formula

R _b SiCl [-b] (I) are reacted,

wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, b and c have the meanings according to one or more of claims 2 to 5.

(Meth) acryloyl-functionalized chlorosilanes of

general formula IV

R _b X ₀ SiCl [4_ (b _{+ c} )] (IV) where R ² , X, b and c have the meanings according to one or more of claims 2 to 5.